Band 11, Heft 2

The aim of this study was to research the seasonal changes of antioxidant enzyme activity and total antioxidant capacity in leaves of Astragalus onobrychis L. subsp. chlorocarpus (Griseb.) S. Kozuharov et D.K. Pavlova. Leaves of A. onobrychis were collected during the different stages of growth and analyzed for antioxidant enzyme activity: superoxide dismutase, catalase, guaiacol peroxidase, glutathione peroxidase. Quantities of malonyldialdehyde, superoxide radicals, and hydroxyl radicals were measured as well as the content of soluble proteins. Furthermore, total antioxidant capacity was determined by the inhibition of chemiluminescence activity of blood phagocytes by leaf extracts. Stages of vegetation significantly affected the accumulation of superoxide radicals, but there were no significant differences in hydroxyl radical quantity and lipid peroxidation levels during vegetation. Soluble proteins vary greatly between different stages of growth. Seasonal changes were found to have an effect on enzymatic activities. During the spring season, guaiacol peroxidase showed the highest levels. Catalase and glutathione peroxidase increased their activities in summer, while, during the autumn season, superoxide dismutase showed maximum activity. On the basis of chemiluminescence assay, it can be concluded that leaf extract of A. onobrychis possesses a significant antioxidant capacity thus protecting plants during environmental stress.

The water-soluble sunscreen 2-phenylbenzimidazole-5-sulfonic acid (PBS) was quantified in a sun-care product and water samples by thin layer chromatography followed by densitometric scanning in fluorescence mode (cut-off filter 370 nm, wavelength of excitation — 300 nm). Normal phase TLC was performed on silica gel 60 as stationary phase. Mobile phase used was ethyl acetate-ethanol-water 70:35:30 (v/v/v). The limit of detection (LOD) was 0.0004 μg spot-1, and the limit of quantification (LOQ) was — 0.001 µg spot−1 without any sample pre-concentration.

Boronic acids and their esters are highly considered compounds for the design of new drugs and drug delivery devices, particularly as boron-carriers suitable for neutron capture therapy. However, these compounds are only marginally stable in water. Hydrolysis of some phenylboronic pinacol esters is described here. The kinetics is dependent on the substituents in the aromatic ring. Also the pH strongly influences the rate of the reaction, which is considerably accelerated at physiological pH. Therefore, care must be taken when considering these boronic pinacol esters for pharmacological purposes.

The present work investigates surface biocompatibility of silicon-substituted calcium phosphate ceramics. Different silicon-substituted calcium phosphate ceramic bodies were prepared from co-precipitated powders by sintering at 1300°C. The in vitro bioactivity of the ceramics was assessed in simulated body fluid (SBF) at 37°C for periods up to 4 weeks. The changes in the surface morphology and composition were determined by scanning electron microscopy (SEM) coupled with electron probe microanalysis and energy dispersive spectrometer (EDX). Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to observe the change in ionic concentration of SBF after removal of the samples. The bioactivity of the ceramics increased with an increasing silicate ion substitution in a systematic way. The surface of ceramics with 2.23% silicon substitution was partially covered with apatite layer after one week, while ceramics with 8.1% silicon substitution were completely covered with apatite in the first week. The porous microstructure of high-concentration Si-substituted ceramics helps the dissolution of surface ions and the leaching process. This allows SBF to reach supersaturation in a short time and accelerate the deposition of apatite layer.

The aim of this work was to implement a chemometric analysis to detect the relationships between the analysed variables in samples of solid fuels. Efforts are being made to apply chemometrics methods in environmental issues by developing methods for the rapid assessment of solid fuels and their compliance with the required emission characteristics regulations. In the present investigation, two clustering techniques—hierarchical clustering analysis (HCA) and principal components analysis (PCA)—are used to obtain the linkage between solid fuel properties and the type of sample. These analyses allowed us to detect the relationships between the studied parameters of the investigated solid fuels. Furthermore, the usefulness of chemometrics methods for identification of the origin of biofuels is shown. These methods will enable control of the degree of contamination.

Activated carbon obtained from bamboo waste was synthesised and modified with iron (BAC-Fe) and used for the removal of arsenic from aqueous solutions. Two different adsorption models were used for analysing the data. The adsorption capacities were determined for BAC-arsenite, BAC-Fe-arsenite, BAC-arsenate and BAC-Fe-arsenate, with a qmax (µg g−1) of 14.89, 19.19, 22.32 and 27.32 respectively. Adsorption capacity varied as a function of pH and modifications to the sorbent. Adsorption isotherms from an aqueous solution of arsenite and arsenates on activated carbons were determined. These adsorption isotherms were consistent with the Langmuir and Freundlich adsorption models. Adsorption kinetics followed a pseudo-first order rate equation, as did the kinetics for BAC-Fe-arsenite and BAC-Fe-arsenate adsorption.

The excited states of cis-trans formic acid dimer and its monomers have been investigated by time-dependent density functional theory (TDDFT) method. The formation of intermolecular hydrogen bonds O1-H1...O2=C2 and C2-H2...O4=C1 induces bond length lengthening of the groups related to the hydrogen bond, while that of the C2-H2 group is shortened. It is demonstrated that the red-shift hydrogen bond O1-H1...O2=C2 and blue-shift hydrogen bond C2-H2...O4=C1 are both weakened when excited to the S1 state. Moreover, it is found that the groups related to the formation of red-shift hydrogen bond O1-H1...O2=C2 are both strengthened in the S1 state, while the groups related to the blue-shift hydrogen bond C2-H2...O4=C1 are both weakened. This will provide information for the photochemistry and photophysical study of red- and blue-shift hydrogen bond.

A simple and reliable novel kinetic method for the determination of piroxicam (PX) was proposed and validated. For quantitative determination of PX, the Bray-Liebhafsky (BL) oscillatory reaction was used in a stable non-equilibrium stationary state close to the bifurcation point. Under the optimized reaction conditions (T = 55.0°C, [H2SO4]0 = 7.60×10−2 mol L−1, [KIO3]0 = 5.90×10−2 mol L−1, [H2O2]0 = 1.50×10−1 mol L−1 and j 0 = 2.95×10−2 min−1), the linear relationship between maximal potential shift ΔE m , and PX concentration was obtained in the concentration range 11.2–480.5 µg mL−1 with a detection limit of 9.9 µg mL−1. The method had a rather good sample throughput of 25 samples h−1 with a precision RSD = 4.7% as well as recoveries RCV ≤ 104.4%. Applicability of the proposed method to the direct determination of piroxicam in different pharmaceutical formulations (tablets, ampoules and gel) was demonstrated.

Using the method of cyclic voltammetry, the electrode process of Ni2+, Pb2+, Cu2+ and pyrocatechin on a poly(o-aminophenol) (PoAP) modified glassy carbon electrode (GCE) was investigated. The PoAP polymer was found to affect the redox process of copper and pyrocatechin. The use of polymer of different thicknesses showed that the obtained film has a dense, nonporous structure. The redox process of the examined substances may be considered as proceeding on the polymer surface. The PoAP polymer obtained in the described conditions takes part in charge transfer.

Retention time of treated water in a horizontal subsurface flow constructed wetland was determined in the non-vegetative period using fluorescein and deuterium oxide. Fluorescein served as one of the most frequent tracers detectable at extremely low concentrations by fluorimetry; however, deuterated water (concentrations of deuterium measured by IRMS and expressed as δ (‰) against VSMOW) was used to precisely simulate the treated water flow movement. Tracer retention time (TRT) of fluorescein was 194 h while deuterated water TRT was 192 h. TRT and nominal hydraulic retention time (nHRT, 190 h) were nearly exactly equal. The tracer behavior of deuterated water was almost ideal. On the other hand, the fluorescein movement through the system was slightly influenced by the interaction with the vegetation bed (sorption causing the tailing of tracer-response curves). Nevertheless, both tracers can be successfully used and provide similar results. Retention time is a very important characteristic of a constructed wetland. It is closely connected with the efficiency of the contaminant removal from treated water. It has to be determined correctly when wetland operation parameters are optimized. The choice of the suitable and reliable tracer is always necessary. Fluorescein takes preference with respect to its simple and inexpensive determination.

Growth processes of nanocomposite layers obtained by polyelectrolytes, poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC), self-assembled on silicon surface using layer-by-layer (LbL) technique were investigated, and theoretical and experimental data are herein reported. Complementary microstructural and compositional analyses techniques (scanning electron microscopy, ellipsometry, X-ray reflectivity, zeta (ξ) potential measurements and attenuated total reflection infrared spectroscopy) were used for deep characterization of the multilayer structure formation. Electrophoretic zeta (ξ) potential measurements indicated that the surface charge was either positive or negative, depending on the polyelectrolyte used (PDADMAC or PSS). ATR-IR spectra confirmed the successfully silanization process and then, the building up of the nanocomposite layer. Morphological investigation and X-ray reflectivity demonstrated the growth process and cross-section size of the bilayers. Ellipsometric measurements were in very good agreement with SEM and XRR, showing once again the successful deposition of polyelectrolyte multilayers.

Materials based on biogenic iron oxides, which are a product of the metabolic activities of the neutrophilic iron-oxidizing bacteria (NIOB) from Sphaerotilus-Leptothrix group, were investigated. Natural microbial probes were collected from freshwater flow from Vitosha Mountain (Bulgaria) and cultivated under laboratory conditions in respect to select suitable cultures and conditions (nutrition media) for biomaterial accumulation of biogenic oxides. Samples were studied by physicochemical methods: X-ray diffraction, Mossbauer spectroscopy and IR spectroscopy. Their phase composition and physicochemical properties were obtained. Presence of both amorphous and crystal phase (ultra- and highly dispersed particles) was proved. Iron-containing compound in the natural biomass consists of α-FeOOH. The cultivated materials have more complex composition with iron-containing ingredients as α-FeOOH, Γ-FeOOH, Γ-Fe2O3 and Fe3O4. The sample of natural biomass was tested in reaction of CO oxidation and it showed potential to be used as catalyst support.

A critical comparison was made of seven solid-phase extraction (SPE) sorbents for the fractionation and isolation of 21 important free and glycosidically-bound varietal volatile aroma compounds. The sample was subjected to SPE and the free aromatics were eluted with dichloromethane followed by elution of the glucoconjugates with methanol; after fractionation, the free fraction was analyzed directly by GC-MS while the sugar-bound fraction was enzymatically hydrolyzed to liberate the free compounds before analysis by GC-MS. The extraction efficiency for the free compounds was evaluated based on the analytes’ signal recovery and for the glycosidically-bound compounds in terms of the relative peak areas. The best results for both the free and bound fractions were obtained with the Isolute ENV+ resin. Following selection of the most efficient SPE material, a GC-MS method was validated (in terms of selectivity, linearity, limits of detection (LODs) and limits of quantification (LOQs), recovery, repeatability, within-laboratory reproducibility and uncertainty) for the quantitative determination of the free primary volatiles in white wines. Validation results are presented at 4 fortification levels (10, 50, 200 and 500 µL−1). Regarding linearity, the correlation coefficient of the matrix-matched calibration plots was ≥0.99 for all the compounds. The LOQs were in the range 0.6–17.5 µg L−1. Recoveries ranged from 61% to 120% while the% relative standard deviation of the within-laboratory reproducibility was in the range 1.3% to 17.7%. Finally, the% expanded uncertainty ranged from 3.1% to 40.3%. The method has been successfully applied to the analysis of 20 white wine samples.

The mechanical, rheological, thermal, and surface behaviors of three polyacrylamide/dextran (PAAm/Dx) semi-interpenetrating polymer network (semi-IPN) hydrogels, prepared at 22°C, 5°C and −18°C, were investigated. The results were compared with those obtained on cross-linked PAAm without Dx synthesized under the same conditions. Hydrogels prepared at the lowest temperature were the most mechanically stable. The thermal stability of the semi-IPN hydrogels is slightly lower than the corresponding PAAm gels, irrespective of preparation temperature. The water vapor sorption capacity depended on the presence of Dx as well as preparation temperature, which determines the network morphology.

Biomass is most often used to produce energy via its combustion and co-combustion along with conventional energy carriers. The prevalence of this method results from the lack of sufficient facilities that can provide a quick and simple chemical classification method, which would show a broader range of possible applications of biofuel in the energy industry. The aim of this study was the development of novel method of classification allowing for quick determine of the direction of the biomass usage by applying classification and regression models of trees (C&RTs). The proper functioning of a C&RT model is based on a very large database of results collected by the Institute for Chemical Processing of Coal during years of work in this field. The created model may be used as decision tool for grouping various biomass sources with respect to their further application in energy generation.

pH-spectrophotometric titration data were used to determine protonation constants of vardenafil at different ionic strengths I and temperatures of 25°C and 37°C. The use of two different multiwavelength and the multivariate treatment of spectral data, SPECFIT32 and SQUAD(84) nonlinear regression analyses and INDICES factor analysis is presented. The reliability of the protonation constants of the drug was proven with goodness-of-fit tests of the pH-spectra. The thermodynamic protonation constants log K Ti were estimated by a nonlinear regression of (log K, I) data using the Debye-Hückel equation, yielding log K 4T = 3.59(1) and 3.26(1), log K 3T = 5.64(1) and 5.81(1), log K 2T = 9.41(1) and 8.59(2), log K 1T = 10.92(2) and 10.05(1) at 25°C and 37°C, where the figure in brackets is the standard deviation in last significant digit. Concurrently, the experimental determination of four thermodynamic protonation constants was combined with the computational prediction of the MARVIN program based on knowledge of the chemical structures of the drug and was in good agreement with its experimental value. The factor analysis of spectra in the INDICES program predicts the correct number of light-absorbing components when the instrument error is known and when the signal-to-error ratio SER is higher than 10.

Complex formation and liquid-liquid extraction were studied in systems containing indium(III), 4-(2-pyridylazo)resorcinol (PAR), phenylmethoxybis(tetrazolium) salt (MBT), water and chloroform. The following MBTs, which differ only by the number of -NO2 groups in their cationic parts, were used: 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)bis(2,5-diphenyl-2H-tetrazolium chloride) (Blue Tetrazolium chloride, BT), 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride] (Nitro Blue Tetrazolium chloride, NBT) and 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)bis[2,5-di(4-nitrophenyl)-2H-tetrazolium chloride] (Tetranitro Blue Tetrazolium chloride, TNBT). The composition of the formed ternary complexes was determined, In:PAR:MBT=1:2:2, and the optimum conditions for their extraction found: pH, shaking time, concentration of the reagents and the sequence of their addition. Some key constants were estimated: constants of extraction (Kex), constants of association (β) and constants of distribution (KD). BT appears to be the best MBT for extraction of the In(III)-PAR species, [In3+(OH)3(PAR)2]4−, (Log Kex=10.9, Log β=9.8, Log KD=1.12, R%=92.7%). Several additional characteristics concerning its application as extraction-spectrophotometric reagent were calculated: limit of detection (LOD = 0.12 µg cm−3), limit of quantification (LOD = 0.40 µg cm−3) and Sandell’s sensitivity (SS =1.58 ng cm−2); Beer’s law is obeyed for In(III) concentrations up to 3.2 µg mL−1 with a molar absorptivity coefficient of 7.3×104 L mol−1 cm−1 at λmax=515 nm.

New complexes of platinum and palladium were isolated with 4-nitrobenzoic hydrazide (4-NH) and characterized by spectroscopic techniques. Results show that the ligand is coordinated to metallic ions by the basic nitrogen of NH2 group and have the general structure cis-[M(4-NH)2X2] where M= Pt or Pd and x = Cl or I. The compound III, [Pt(4-NH)2I2], was found to display cytotoxicity (IC50 = 0.96 µmol L−1) against the K562 tumoral cell line. This complex is significantly more cytotoxic than cisplatin.

The present work focused on the qualitative and quantitative analysis of Cr detoxification strategy of aquatic cosmopolitan plant Callitriche cophocarpa. This plant species has just been described in the context of its unusual accumulation potential of Cr. The emphasis of the work was placed on the redox reaction Cr(VI)→Cr(III) which is considered to be remediation mechanism of highly reactive and mobile Cr(VI) ions. Plants were immersed for 5 days in 1 mM of Cr(VI) (potassium dichromate) or 1 mM of Cr(III) (chromium sulphate) solutions in semi-natural conditions. Cr was effectively removed from the solution up to the extent of ca.58% or 35% of the starting amount, in the case of Cr(III) and Cr(VI), respectively. No plant-induced Cr(VI) reduction accompanying Cr accumulation was observed in Cr(VI) solutions except from the apparent one, noticed at the fourth day of incubation. On the contrary to these results, according to the method of electron paramagnetic resonance spectroscopy (L-band EPR), biphasic signal of Cr(V) attending Cr(VI) to Cr(III) reduction was detected inside the plant tissue every day of investigations. Our results show that phytoextraction but not phytostabilization is the main strategy of Cr detoxification by C. cophocarpa in aquatic systems.

Nickel catalysts supported on Na-mordenite were used for paraffin LTP56-H hydroconversion into liquid material as a possible component for engine fuels. The effects of none-catalytic thermal treatment and catalytic conditions-zeolite type and reaction conditions (solvent) on the process of liquefaction of LTP56-H paraffin and physicochemical properties of catalysts were studied. The physicochemical properties of catalytic systems were investigated using XRD, TPR, TPD-NH3 and SEM-EDS methods.

In this study, the effect of the increase in the initial concentration of Na(I) ions in the solution during biosorption of Cr(III) ions by two edible algae: marine macroalga — Enteromorpha prolifera and microalga — Spirulina sp. was investigated. During biosorption, essential elements are exchanged with alkali and alkaline earth metal ions (e.g. Na(I) ions), which are naturally bound with the biomass. The goal of this study was to investigate the effect of the increase in concentration of Na(I) ions on biosorption performance. The equilibrium of the process is described by Langmuir equation. It was found that with the increase in the initial concentration of NaCl (from 132 to 7331 mg L−1), there was a lower biosorption capacity of Enteromorpha prolifera (from 85.8 to 51.0 mg g−1) and Spirulina sp. (74.2 to 20.7 mg g−1) towards Cr(III) ions. It was also possible to determine the number of times the solution used in the biosorption process can be recycled and yet mantain high biosorption capacity. The determined numbers were: 16 for Enteromorpha prolifera and 19 for Spirulina sp.

An electrochemical biosensor based on a supported polymerized lipid film with incorporated sheep anti-3,3′,4,4′ tetrachlorobiphenyl (PCB congener 77) antibody using flow injection analysis was developed. The polymerized lipid film contained 85% (w/w) dipalmitoylphosphatidylcholine (DPPC) and 15% (w/w) dipalmitoylphosphatidic acid (DPPA), methacrylic acid, ethylene glycol dimethacrylate, AIBN and sheep anti-congener 77 antiserum. Congener 77 was injected into flowing carrier electrolyte and the flow stopped to detect the antigen. These membranes gave only a single transient proportional to log [congener 77] from 10−8 to 10−5 M, with a detection limit of ca. 10−8 M. A membrane containing 35% (w/w) DPPA was used to examine regeneration. The maximum number of cycles was about 5.